Thorium-mediated ring-opening of tetrahydrofuran and the development of a new thorium starting material: preparation and chemistry of ThI(4)(DME)(2).

MedLine Citation:

PMID:
23027565
Owner:
NLM
Status:
Publisher

Abstract/OtherAbstract:

The thorium(iv) tetraiodide complex ThI(4)(DME)(2) () (DME = 1,2-dimethoxyethane) has been prepared in high yield by reacting the corresponding chloride complex ThCl(4)(DME)(2) with an excess of trimethylsilyl iodide (Me(3)SiI) in toluene. This new route avoids the use of thorium metal as a reagent. ThI(4)(DME)(2) () exhibits excellent thermal stability compared to ThI(4)(THF)(4) (), which undergoes rapid ring-opening of THF at ambient temperature to yield the iodobutoxide complex ThI(3)[O(CH(2))(4)I](THF)(3) (). Subsequent ligand-exchange between and DME affords ThI(3)[O(CH(2))(4)I](DME)(2) (), which can be converted to with Me(3)SiI. Salt metathesis between and K(L(Me)) (L(Me) = (2,6-(i)Pr(2)C(6)H(3))NC(Me)CHC(Me)N(2,6-(i)Pr(2)C(6)H(3))) cleanly gives (L(Me))ThI(2)[O(CH(2))(4)I](THF) (), which is a rare example of a thorium β-diketiminate complex. Complexes , , and represent the first reported examples of THF ring-opening mediated by thorium. The synthetic utility of ThI(4)(DME)(2) () is demonstrated by preparation of thorium(iv) alkoxide, amide, and organometallic compounds.